Novel photographic products and processes employing anthraquinone dye



United States Patent F 3,135,606 NOVEL PHOTOGRAPHIC PRODUCTS 'AND PROC-ESSES EMPLOYING ANTHRAQUIN ONE DYE Elkan R. Blout, Belmont, Marilyn R.Cohler, Brookline, Milton Green and Myron 5. Simon, Newton Center, andRobert B. Woodward, Belmont, Mass., assignors to Polaroid Corporation,Cambridge, Mass., a corporation of Delaware No Drawing. Filed Oct. 26,1962, Ser. No. 233,461 38 Claims. (Cl. 9629) This invention relates tophotography and more particularly to products, compositions andprocesses for the development of photosensitive silver halide elements.

It is one object of the present invention to provide novel processes andcompositions for the development of silver halide emulsions, in whichnovel colored developing agents are used to develop a latent image.

Another object is to provide novel processes and compositions for thedevelopment of silver halide emulsions, in which the novel developingagent is capable of develop mg a latent image and imparting a reversedor positive colored image of said latent image to a superposedimagereceiving material.

A further object is to provide novel products, processes andcompositions suitable for use in preparing monochromatic andmultichromatic photographic images.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the processes involving the severalsteps and the relation and order of one or more of such steps withrespect to each of the others, and the products and compositionspossessing the features, properties and the relation of elements whichare exemplified in the following detailed disclosure, and the scope ofthe application of which will be indicated in the claims.

The objects of this invention may be accomplished by the use of certainnovel dyes which have the ability to develop latent images present in anexposed silver halide emulsion; thus they may be referred to as dyedevelopers. These novel dyes or dye developers Will be further describedhereinafter.

The photographic processes and compositions disclosed herein areparticularly useful in the treatment of a latent image present in aphotosensitive element, such as an exposed silver halide emulsionwhereby a positive dye image thereof may be imparted to another element,herein referred to as an image-carrying or image-receiving'element.

US. Patent No. 2,983,606, issued May 9, 1961, to Howard G. Rogers,discloses diffusion transfer reversal processes wherein a photographicnegative material, such as a photographic element comprising an exposedsilver halide emulsion layer containing a latent image, is developed inthe presence of a dye developer to impart to an image-receiving elementa reversed or positive dye image of said latent image by permeating intosaid emulsion layer a suitable liquid processing composition andbringing said emulsion layer into superposed relationship with anappropriate image-receiving layer. The inventive concepts. herein setforth provide novel dye developers for use in such processes.

3,135,606 Patented June 2, 1964 element is brought into superposedposition with an image-receiving element. The liquid processingcomposition permeates the emulsion to provide a solution of dyedeveloper substantially uniformly distributed therein. As the latentimage is developed, the oxidation product of the dye developer isimmobilized or precipitated in situ with the developed silver, therebyproviding an image- Wise distribution of unoxidized dye developerdissolved in the liquid processing composition. This immobilization isapparently due, at least in part, to a change in the solubilitycharacteristics of the dye developer upon oxidation, and especially asregards its solubility in alkaline In carrying out the process of thisinvention, a photosensitive element containing a silver halide emulsionis exposed and Wetted with a liquid processing composition, for exampleby immersing, coating, spraying, flowing, etc., in the dark, and thephotosensitive element superposed, prior to, during or after wetting, onan imagereceiving element. In a preferred embodiment, the photosensitiveelement contains a layer of dye developer, and the liquid processingcomposition is applied to the photosensitive element in a uniform layeras the photosensitive solutions. It may also be due, in part, to atanning effect on the emulsion by the oxidized developing agent. Atleast part of this imagewise distribution of unoxidized dye developer istransferred, by imbibition, to a superposed image-receiving element,said transfer substantially excluding silver or oxidized dye developer.The latter element receives a depthwise diffusion, from the emulsion, ofunoxidized dye developer, without appreciably disturbing the image-wisedistribution thereof, to provide a reversed or positive, coloredimage ofthe negative image. The image-receiving element may contain agentsadapted to mordant or otherwise fix the diffused, unoxidized dyedeveloper. Imbibition periods of approximately one minute have beenfound to give good results, but this contact period may be adjustedwhere necessary to compensate for variations in temperature or otherconditions. The desired positive image is revealed by stripping theimagereceiving element'from the photosensitiveelement at the end of theirnbibition period.

The dye developers of this invention may be utilized in thephotosensitive element, for example, in, on or behind the silver halideemulsion, or they may be utilized in the image-receiving element or inthe liquid processing composition. In a preferred embodiment, a coatingor layer of the dye developer is placed behind the silver halideemulsion, i.e., on the side of the emulsion adapted to be located mostdistant from the photographed subject when the emulsion is exposed andpreferably also adapted to be most distant from the image-receivingelement when in superposed relationship therewith. Placing the dyedeveloper behind the emulsion layer, as in the preferred embodiment, hasthe advantage of providing increased contrast in the positive image, andalso minimizes any light-filtering action by the colored dye developer.In this preferred embodiment, the layer of dye developer may be appliedby using a coating solution containing about 0.5 to 8%, by weight, ofthe dye developer. Similar concentrations may be used if the dyedeveloper is utilized as a component of the liquid processingcomposition. In an especially useful mode of disposing the dyedevelopers in the photosensitive elements, the dye developer isdissolved in a water-immiscible solvent and then dispersed in a gelatincoating solution. The coating solution is then applied to thephotosensitive element, which is to be prepared, in the sequencedesired.

The liquid processing composition which is used in the processes hereindisclosed comprises at least an aqueous solution of an alkalinecompound, for example, diethylamine, sodium hydroxide or sodiumcarbonate, and may contain the dye developer. In some instances, it maycontain a conventional developing agent. If the liquid processingcomposition is to be applied to the emulsion by being spread thereon,preferably in a relatively thin, uniform layer, it may also include aviscosity-increasing compound constituting film-forming material of thetype which, when spread over a water-absorbent base, will form arelatively firm and relatively stable film. A prefered film-formingmaterial is a high molecular weight polymer such as a polymeric,water-soluble ether inert to s,135,soe

9 an alkali solution, as, for example, a hydroxyethyl cellulose orsodium carboxymethyl cellulose. Other filmforming materials whoseability to increase viscosity is substantially unaffected when insolution for a long period of time may also be used.

The novel dye developers of this invention are aminoanthraquinone dyeswhich have a developing moiety or moieties joined to an aminosubstituent substituted directly on the anthraquinone nucleus through abivalent organic radical comprising at least one methylene group. Thesedye developers may be defined as anthraquinone dyes, in which at leastone and not more than two of the nuclear carbon atoms of theanthraquinone nucleus of said dye have linked directly thereto a radicalof the formula:

wherein Z is a bivalent organic radical containing at least onemethylene (--CH group, preferably a lower alkylene group such asmethylene, ethylene, isopropylene, etc.; and X is a benzenoid silverhalide developing radical and is preferably a dihydroxyphenyl silverhalide developing radical such as p-dihydroxyphenyl, o-dihydroxyphenyl,and suitably substituted derivatives thereof.

The anthraquinone nucleus may and in general will contain othersubstituents which impart specific desired chemical and/or physicalcharacteristics to the dye, e.g., substituents which contribute to thespectral absorption characteristics of the compound. Such othersubstituents are well known in the dye art and per se comprise no partof the present invention.

One class of dye developers within the scope of Formula 1 may berepresented by the following formula:

wherein A is an anthraquinone nucleus; each Y may be a hydrogen, amino,alkyl, aryl, halogen, alkylamino, especially hydroxyalkylamino, andhydroxy-sec-alkylamino, arylamino, aryloxy, alkoxy, hydroxyl, sulfonamido, alkylsulfonamido, arylsulfonamido, carboxamido, nitro, carboxyl orsulfo radical; in is a positive integer less than and preferably lessthan 3; and Z and X have the meanings heretofore given in Formula 1.

The dye developers of this invention, as illustrated by Formulae 1 and1a, are further characterized in that the only developing moiety presentin the dye developer molecule is that present in the NHZ--X substituent.In this respect, the novel dye developers of this invention aredistinguished from those dye developers disclosed and claimed in US.Patent No. 2,983,605, issued on May 9, 1961, to Richard S. Corley. It isto be noted, however, that, as is stated in the above-mentioned patent,the dye developers of this invention are also useful as intermedi atesin the preparation of the acylated dye developers of said patent.

One class of dye developers within the scope of the invention asillustrated by Formulae 1 and 1a and which have been found to beparticularly useful are those wherein m is 2 and the NH--Z-X radicalsare substituted in the 1 and 4 positions.

Such developers may be represented by the formula:

ll I IH-L-X wherein Y, Z, and X have the meanings heretofore noted andeach Z and X may be the same or different.

Another class of dye developers within the scope of this invention whichhave been found particularly useful are those wherein m is 1, the--NHZ-X radical is substituted in the 1 position and Y in the 4 positionis substituted by an alkylamino group. In a preferred embodiment thealkylamino group is a hydroxyalkyl amino O NH-R wherein Y, Z, X are thesame as above and R is an alkyl, preferably a hydroxyalkyl and morepreferably a hydroxy-sec-alkyl group.

Still another class of developers within the scope of this inventionwhich have been found particularly useful are the compoundscorresponding to the compounds within Formulae 2 and 3 wherein Y in the5 and 8 positions is a hydroxy group.

The expression bivalent organic radical, as used herein refers toorganic radicals having two valences available for joining two atoms orradicals. As examples of bivalent organic radicals comprehended by theradical Z,

mention may be made of alkylene radicals such as CH CH i -OH CH- as wellas alkarylene bivalent radicals such as It is also intended that Z maybe saturated, unsaturated, such as CH CH=CHCH or substituted, such aschloroalkylene or hydroxyalkylene. Experience has indicated that where Zis an alkylene group, best results are obtained by the use of a loweralkylene group, e.g., an alkylene group containing less than about sixcarbons, and preferably an isopropylene OH--CI-I (EH3 group. It shouldbe understood that Z may be an alkylene group comprising six or morecarbon atoms provided that the resulting dye developer is capable ofbeing dissolved in the liquid processing composition described herein,and its oxidation product rendered immobile.

The copending application of Elkan R. Blout and Myron S. Simon, SerialNo. 449,514, filed August 12, 1954, (now abandoned) discloses and claimscertain novel dye developers containing an anthraquinone ring similar tothose set forth above. The dye developers herein disclosed and claimedmay be distinguished therefrom in that the dye developers of the presentapplication contain the bivalent organic radical Z, and such dyedevelopers have been found to be photographically superior to those setforth in the above-mentioned application, especially as regards theirbrightness and purity of color. Moreover, particularly when Z is a loweralkylene group, there is a substantial unexpected increase in thedensity of the transfer images. The increase in density is especiallymarked when Z is a secondary alkylene group, e.g., an isopropylene groupand more particularly when the secondary carbon atom of such secondaryalkylene groups is adjacent the amino group. It is believed that thissuperi ority is attributable to the ability of the bivalent organicradical to insulate the silver halide developer radical from theamino-substituted anthraquinone.

The novel dye developers of this invention may be prepared by thereplacement of 'sulfo, halogen, nitro, hydroxyl, alkoxy or aminosubstituents on anthraquinone nuclei by amino groups derived from amineshaving the formula:

aims:

wherein Z and X have the same meaning as set forth above.

The 1 and 4 substituted anthraquinones such as those represented byFormulae 2 and 3 may be conveniently prepared from1,4-diaminoanthraquinones and from 1,4- dihydroxyanthraquinones, i.e.,quinizarins. When quinizarin is used in the preparation of thecompounds, herein disclosed, the quinizarin may be first reduced toleuco quinizarin, then condensed, and the resulting product oxidized tothe anthraquinione, by for example, aerial oxidation. When it is desiredto prepare the dye developers herein disclosed directly from quinizarinit has been found that the reaction may be facilitated by carrying itout in the presence of an acid-acceptor and a monohydroxy-substitutedaryl compound. As examples of monohydroxy-substituted aryl compounds,mention may be made of phenol, naphthol, cresol, xylol, etc. It has beenfurther found that the condensation of quinizarin with the amine mayalso be facilitated by carrying the reaction out in the presence of anacid-acceptor and an ortho or para-dihydroxy-substituted aryl compound.As examples of orthoand para-dihydroxy-substituted aryl compounds,mention may be made of hydroquinone, catechol, naphthohydroquinone, and1,2-dihydroxynaphthalene. H

The dye developers within Formula 3 may be prepared by condensing ananthraquinone such as quinizarin with about an equivalent of an aminewithin Formula 4 and then with about an equivalent of an amine withinformula:

wherein R is the same as above. It will be understood that the order ofcondensing the amines may be reversed to suit particular needs. It Willbe further understood that dye developers within Formula 2 wherein theNHZX radicals are different may be similarly prepared.

The compounds within the scope of this invention may be further preparedby condensing an amino-substituted anthraquinone with ahaloalkyl-substituted benzenoid silver halide developer;

It should be noted that the process of this invention permits one toconvert compounds which are not dyes into products which are both dyesand photographic developing agents.

In certain instances, in using the dye developers herein disclosed inphotographic processes, it may be desirable to temporarily shift thelight absorption characteristics of such dye developers so that theyabsorb less light of the higher wave lengths. One such instance whensuch a shift is desirable occurs when a cyan dye developer, such as the1,4-diamino-substituted developers disclosed herein, are disposed inred-sensitive silver halide emulsions. In such a use it may be desirablethat said dye developers absorb less red light until at least afterexposure. In instances such as this and in other instances where such ashift is desirable, it has been found that the leuco-form of theanthraquinones may be employed.

When it is desired to shift the color back, such as, for example, afterexposure or transfer, such a shift may be made by a simple oxidation,e.g., aerial oxidation.

X has been defined as a benzenoid silver halide developing radical. Suchbenzenoid silver halide developers in general comprise an aryl nucleuswhich is substituted by at least two substituents selected from thegroup consisting of amino, alkylamino, and/or hydroxyl groups. Theamino, alkylamino, and hydroxyl substituents are usually substituted inorthoor para-relationship with respect to each other, however, inpolynuclear benzenoid developers they may be substituted in differentrings. When substituted in different rings the positions which suchsubstituents must occupy with respect to each other in order to providea developing function are known from texts, such as, for example, TheTheory of the Photographic Process, C. E. K. Mees, (revised edition,1954), The Macmillan Co., New York, N.Y., p. 544 et seq. In a preferredembodiment of this invention the benzenoid silver halide developingradical is selected from those comprising dihydroxy-substituted benzeneor naphthalene nuclei and more preferably comprises an orthoorparadihydroxybenzene radical. The para-dihydroxybenzenes have been foundparticularly useful. It should be noted that the radical X may c0ntainsubstituents other than those which supply the silver halide developingfunction so long as such substituents donot adversely affect the silverhalide developing ability; such substituents include alkyl, alkoxy,hydroxy, amino, halogen, etc.

Where the developing function possessed by X is supplied by hydroxyl oramino groups, it may be desirable to protect these groups, duringsynthesis, as by acylation, to avoid side reactions or oxidation. Theprotective groups are removed, as by hydrolysis, prior to photo graphicuse As examples of dye developers ithin the scope of this invention,mention may be made of:

on I a I NIL-CH-OH O lA-bis-I amethyl-B-hydroqulnonyl-ethylarniuo)-anthraquinone NH- H-CHr- I I III1,4-b1sa-methyl-B-hydroquinonyl-ethylamino -5,8-

. dihydroxyanthraquinone CHz-OH NH-CH-CHz-OH;

1- a-hydroxymethyl-propylamino) -4- a-methyl-fi-hydroquinonyl-ethylamino-anthraquinone 1-(a-hydroxymethyl-propylanin'o)-4-(a-methy1-Q-hydroquinonyl-ethylamino)-5,8-d1hydroxyanthraqu1none Other dye developers which have beenprepared and are illustrative of the compounds within the scope of thisinvention include:

1-hydroxy-4.- (a-methy1-hydroquinonylethylamino anthraquinone.

1,4-bis- ('y-hydroquinonyl-a-methyl-propylamino) -5,8-

dihydroxyanthraquinone.

1,4-bisa-methyl-v-hydroquinonylpropylamino) anthraquinone.

1, -bis-hydroquinonylmethylamino-anthraquinone.

1,4-bis-hydro quinonylmethylamino-anthraquinone1,4-bisa-methyl-5-hydroquinonylethylamino -6,7-

dichloroanthraquinone.

1- a-methyl-fi-hydro quinonylethylamino -4-(or-ethylfi-hydroquinonylethyl amino -anthraquinone.

1- a-methyl-,8-hydroquinonylethylamino) -4- (a-ethyl-B-hydroquinonylethyl amino) -5, S-dihydroxyanthraquinone.

1 ,4-bis- (a-methyl-2,5 '-dihydroxybenzyl amino) anthraquinone.

1,4-bisa-methyl-fl-hydroquinonylethylamino -5,8-

bis-benzene-su1fonamido-anthraquinone.

1,4-bis- (ot-methyl-fi-hydro quinonylethylamino -5-hydroxy-8-amino-anthraquinone.

1- (ot-hydroxymethyl-propylarnino -4-(a-methyl-B-hydroquinonylethylamino) -5 -hydroxyanthraquinone.

1,4-bisot-methyl-B-hydroquinonylethylamino -5- hydroxyanthraquinone.

1,4-bis- B-hydro quinonyl-ethylamino) -anthraquinone.

1- p- B-hydro quinonyl-ethyl -phenylamino] anthraquinone.

1- (a-hydroxymethyl-propylamino -4- 13- 4-methy1- 2 ,5'-dihydroxyphenyl) -a-methyl-ethyl amino] anthraquinone.

1-ethylamino-4- ,6- 3 ',4-dihydroxyphenyl) -ethylamino] -anthraquinone.

1-chloro-4- B-hydroquinonylethyl amino) -anthraquinone.

l-hydroxy-4- [,8- 3',4'-dihydroxyphenyl -ethylamino] anthraquinone.

1-chloro-5-(fi-hydroquinonylethylamino)-anthraquinone.

1,4-bis- [fi- 3 ',4'-dihydroxyphenyl) -ethylamino] -5,8-

dihydroxyanthraquinone.

1,8-bis- [p- (3 ',4'-dihydroxyphenyl -ethylamino] anthraquinone.

1- [B- (3 ,4'-dihydroxyphenyl) -ethylamino] anthraquinone.

1-,B-hydroquinonylethylamino-anthraquinone.

1,5 -bis- 8- 3',4'-dihydroxyphenyl) -ethy1amino] anthraquinone.

1,5-bis- (lit-hydro quinonylethylamino) -anthraquinone.

1, 8-bis- 8-hydroquinonylethylamino -anthraquinone.

1- p- (3 ,4-dihydroxyphenyl -ethylamino] -5-nitroanthraquionne.

1, 5 -bisa-methyl-fi-hydroquinonylethyl amino anthraquinone.

1- B-hydroxyethyl amino) -4- (B-hydroquinonylethylamino) -anthraquinone.

1,4-bis- [fi- 3 ,4'-dihydroxyphenyl -ethylamino] anthraquinone.

1- (B-hydroxyethylamino -4- (a-methyl-fi-hydroquinonylethylamino)-5,8-dihydroxyanthraquinone.

8 1 ,4-bis- (a-ethyl-fl-hydro quinonylethylamino) anthraquinone.1-methylamino-4- (fl-hydroquinonylethylamino anthraquinone.l-p-hydroxyethyl amino-4- a-methyl-fl-hydroquinonylethyl amino-anthraquinone.

The following nonlimiting examples illustrate the preparation of dyedevelopers within the scope of this invention.

Example 1 One mole of leucoquinizarin and four moles of 4-(beta-arninoethyl)-catechol hydrobromide are refluxed in butanol forfour hours under nitrogen in the presence of four moles of sodiumbicarbonate. The reaction mixture is then acidified with dilutehydrochloric acid (in the presence of sufiicient methanol to maintain asingle liquid phase) and filtered. The precipitate is oxidized bydissolving in pyridine open to the air and boiling until no furthercolor change takes place. Crystallization from ethyl acetate-petroleumether yields 1,4-bis-[beta-(3',4- dihydroxyphenyl -ethylamino]-anthraquinone, melting at 159-161 C. This compound is soluble inacetone, ethyl alcohol, ethyl acetate and pyridine, and insoluble inwater and petroleum ether. It is stable in neutral or acid solution, butunstable in base in the presence of air. Analysis of the product shows:

C I-IlN Example 2 Leucoquinizarin (1.2 g.; 0.005 mole),Z-beta-aminoethyl)-hydroquinone hydrobromide (2.8 g.; 0.012 mole), andsodium bicarbonate (0.01 g.; 0.012 mole) are refluxed in 25 ml. ofpyridine for two hours under nitrogen. One ml. of concentratedhydrochloric acid and one ml. of water are added to the reaction mixtureand air is bubbled through at the reflux point until the color of thereaction mixture has gone to a clear blue without traces of green color.The reaction mixture is filtered into 150 ml. of 10% hydrochloric acid,the filtrate cooled in ice, and filtered. The solid is washed with waterand ethyl acetate and then dissolved in ethanol and concentrated (undernitrogen) to give 0.5 g. (32% yield) of 1,4 bis (beta hydroquinonylethylamino) anthraquinone melting at 154-157 C. Concentration of themother liquor gives an additional yield of 1.03 g. of product of lesserpurity. The product in an ethanol solution is pure blue in color indaylight. It is slightly soluble in acetone and ethyl acetate, solublein alcohol and pyridine but insoluble in water and petroleum ether. Itis stable in neutral or acid solution, but unstable in base in thepresence of air. Nitrogen analysis of the product shows a nitrogen valueof 5.8% as compared with a calculated value of 5.5%.

It has been found that the yield of the desired 1,4-bis- [beta (2',5'dihydroxyphenyl) ethylamino] anthraquinone may be increased, and itspurification simplified, by increasing the reaction time, as illustratedby the following example:

Example 3 Leucoquinizarin (2.3 g.; 0.0097 mole),Z-(beta-aminoethyl)-hydroquinone hydrobromide (5 g.; 0.021 mole), andsodium bicarbonate (1.8 g.; 0.021 mole) are refluxed, under nitrogen,for 21 hours in cc. of pyridine and 3 cc. of water. The reaction mixtureis then cooled below the boiling point. A 1:1 concentrated hydrochloricacid and water mixture (4 cc.) is added. Air is bubbled through themixture at the refiux point until the color of the mixture has gone to aclear blue without traces of a green color. The solution is cooled andthen filtered into excess 10% hydrochloric acid. The resultingprecipitate is filtered, Washed with water, and pulverized. Thepulverized product is washed with hot alcohol to obtain 3 g. (60.3%yield) of the desired 1,4-bis-[betahydroquinonyl-ethylamino]-anthraquinone. The ethanol washings areprecipitated with water and the precipitate washed with hot ethanol toobtain an additional 0.3 g. of the desired product.

Although hydrobromide salts of the H-NZ-X compounds have-been used inthe above'examples, the

free amine or other salts thereof, e.g., the hydrochloride, may be used.

Example 4 12 g. leucoquinizarin (0.05 mole), 32.2 g. sodium bicarbonateand 25 g. of 2-aminopropylhydroquinone-hydrobromide were placed in 375cc. of nitrogen-deaerated pyridine and 10 cc. of water and refluxedovernight under vacuum. 8 cc. of a 50% hydrochloric acid solution wereadded and air was bubbled into the solution over a steam bath for aboutan hour until a blue solution resulted. The product wasprecipitated'into dilute hydrochloric acid and purified twice fromacetone into water. The resulting precipitate was further washed with a5 to acetonewater solution until the washings no longer showed ayellow-brown color. The product was heated with 300 cc. of ethyl acetateuntil most of it dissolved. The undissolved material -was1-.(B-hydroquinonyl-a-methyl-ethylamino)-4-hydroxy-anthraquinone. Theethyl acetate solution was concentrated under nitrogen to about 80 cc.and precipitated into hexane. The ethyl acetatehexane purification wasrepeated and then followed with a crystallization from a (4 to 6 byvolume) water-ethyleneglycol monomethyl ether solution. The1,4-bis-(B-hydroquinonyl-a-methyl-ethylamino) -anthraquinone producedsinters at 130 to 132 C. and a spectrographic analysis showed thefollowing:

The following Example 5 provides an alternative method for preparing thecompound of Example 4 using quinizarin.

Example 5 2.4 g.'quinizarin (0.01 mole), 8.6 g.,d-amino-a-methylethylhydroquinone-hydrobromide (0.035 mole), 0.34 g.sodium carbonate, 3.4 phenol (0.036 mole), 12 cc. 95% ethanol and 8 cc.of water were mixed together and deaerated with nitrogen. The mixturewas then refluxed under nitrogen for 72 hours, then cooled and washedout of the reaction flask with a dilute hydrochloric acid solution intoice water. The resulting precipitate was filtered, washed several timeswith warm water and dissolved in acetone. The acetone solution wasfiltered and poured with rapid stirring into a large volume of an iced2% hydrochloric acid solution. The resulting precipitate was warmed on asteam bath to 40 C. to aid coagulation, filtered while still warm andwashed with water. The product was purified twice from acetone intohexane and dried under a heat lamp.

Example 6 5.5 g. of 5,8-bis-benzenesulfonamide-quinizarin (0.01 mole),9.95 g. of El-amino-a-methyl-ethylhydroquinonehydrobromide (0.04 mole),1.8 g. of sodium carbonate, 3.4 g. of sodium bicarbonate and 3.75 g.phenol were placed in a deaerated flask, mixed with a nitrogen deaeratedsolution comprising 17 ml. of 95% ethanol and 11.5 ml. of water andreacted under nitrogen at a temperature of 105-7 C. for 101 hours. Thereaction mixture was precipitated into a 2% hydrochloric acid solutionfiltered, and the resulting precipitate was redispersed in a 2%hydrochloric acid solution. The precipitate was then filtered and washedwith a 2% hydrochloric acid solution until the washings were colorless.The product was then precipitated from ethyleneglycol monomethyl etherto di-' lute hydrochloric acid, filtered and dried. The product wasfurther purified by twice precipitating it from ethyl acetate intohexane. The 5,8-bis-benzenesulfonamido-1,4-bis-(B-hydroquinonyl-a-methyl-ethylamino) anthraquinone producedsintered at 142 C., and, upon a spectrographic analysis inethyleneglycol monomethyl ether, showed the following:

e 672 Inu=19,200 e 622 mu=l4,000 e 580 m,u=.l1,600

Example 7 2.3 g. of leuco-1,4,5,8-tetrahydroxyanthraquinone, 5.6 g. of2-aminopropyl-hydroquinone hydrobromide and 1.9 g. sodium bicarbonatewere dissolved in 50 ml. of pyridine and 2 ml. of water and refluxed for64 hours. The solution was aerated at its boiling point for 1.2 hoursand then allowed to stand at room temperature for an additional 18hours. The product was precipitated into a 10% hydrochloric acidsolution and taken up in 300 ml. of methanol. The methanol solution wasevaporated until crystallization began and then it was allowed to standovernight. The1,4-bis-(fi-hydroquinonyl-u-methylethylamino)-5,8-dihydroxyanthraquinoneproduced had a melting point of 224 C. and upon a spectrographicanalysis showed the following:

6 620 m .=20,600 e 675 m =3o,00q

Example 8 36.0 g. quinizarin (0.15 mole) and 50 g. phenol were added to180 ml. of ethanol and ml. of water and deaerated with nitrogen. 5 g. ofsodium carbonate and 13.4 g. of Z-amino-l-butanol (0.15 mole) were addedand the mixture was refluxed for 40 minutes under nitrogen. 37.2 g. of2-aminopropylhydroquinone-hydrobromide (0.15 mole) and 12.6 g. sodiumbicarbonate were then added and refluxing was continued under nitrogenfor another 22 hours until the reaction was completed. The reactionmixture was poured into 10% hydrochloric acid yielding a gummy mass. Thegummy mass was purified twice from acetone into dilute hydrochloric acidand then from ethyleneglycol monoethyl ether into dilute hydrochloricacid. The mass was further purified twice from ethylacetate into hexaneand dried in a vacuum desiccator. The 1-(a hydroxymethyl propylamino) 4(B-hydroquinonyl oz methylethylamino)-anthraquinone obtained showed thefollowing in a spectrograph analysis;

6 640 mp: 19,000 6 594 m,u=16,400 e 558 m,u=8,800

Example 9 313.7 g. of leuco 1,4,5,8 tetrahydroxyanthraquinone (0.0 5mole), 12.4 g. of Z-aminopropylhydroquinohe-hy:- drobromide (0.05 mole)and 4.2 g. of sodium bicarbonate (0.05 mole) were added .to ml. ofpyridine and refluxed for 24 hours under nitrogen. 5.0 g. of2-aminobuta-nol (0.056 mole) were added and the refluxing was continuedanother 24 hours under nitrogen. 5 cc. of concentrated hydrochloric acidwas added and air was bubbled through the solution at 7085 C. for about24 hours. The mixture was cooled and added to a solution comprising 3000ml. of water and 250 ml. of concentrated hydrochloric acid. Theresulting precipitate was filtered oif and washed with cold water untilthe filtrate was colorless. The solid was vacuum dried, powdered andmixed with 1 to 2 volumes of celite and extracted with 200300 ml. ofethyl acetate in a Soxhlet extractor until the extract was nearlycolorless. Upon cooling, the extract was stirred into about 2500 m1. ofhexane and the resulting precipitate was filtered and dried. The l-(oc-11 hydroxymethyl-propylamin'o) 4 ([3 hydroquinonyl-a methyl-ethylarnino)5,8 dihydroxyanthraquinone produced, showed, upon a spectrographicanalysis, the following:

Example 2.56 g. of 1,4,5-trihydroxy-anthraquinone (0.01 mole), 8.6 g. of2 aminopropylhydroquinone hydrobromide (0.036 mole), 0.34 g. of sodiumcarbonate, 2.9 g. sodium bicarbonate (0.36 mole) and 3.4 g. of phenolwere added to ml. of water and ml. of ethanol and refluxed undernitrogen for 49 hours. The reaction mixture was poured into a 15%hydrochloric acid solution and the resulting precipitate was filteredand washed several times with water. To insure the absence of leucomaterial the precipitate was dissolved in boiling pyridine in air, thenprecipitated into dilute hydrochloric acid. The resulting gummy solidwas precipitated from acetone into hexane and dissolved in methylacetate. The methyl acetate solution was concentrated and, on cooling,the product crystallized out in microneedles. The product was filtered,washed several times with methyl acetate containing enough hexane toprevent solubilization, and dried at room temperature overnight.(fl-hydroquinonyl-a-methyl-ethylamino) anthraquinone produced melted at1506 C. and showed the following in a spectrographic analysis usingethylene-glycol monoethyl ether as the solvent:

6 655 I11,u=26,600 e 604 mar- 19,200

Example 11 e 657 III/4:21AM) An elemental nitrogen analysis showed thefollowing:

Percent Calculated 4.63 Found 4.4

Example 12 1.4 g. of 1,8-dichloroanthraquinone, 5.9 g.p-aminoethylhydroquinone-hydrobromide and 2.1 g. sodium bicarbonate wereadded to 15 cc. of qulnoline and refluxed for 4 /2 hours under nitrogen.The reaction mixture was added to dilute hydrochloric acid and ice,filtered and washed with dilute hydrochloric acid. The precipitate wasdissolved in ethyl alcohol under nitrogen, and the resulting ethylalcohol solution was filtered and concentrated under nitrogen. Theresulting crystalline product was filtered and washed with a smallamount of cold ethanol. The product was still further purified bycrystallization from ethanol under nitrogen. The resulting1,8-bis-(fihydroquinonylethylamino) anth'raquinone sintered at 163-8 C.and upon a spectrographic analysis, using dimethyl formamide as thesolvent, showed the following:

a 545 mp.=7,500

Example 13 1.2 g. of 1,S-dichloroanthraquinone, 6.0 g.fl-aminoethylhydroquinone and 5.8 g. of sodium bicarbonate were added to130 cc. of quinoline and reacted at reflux for three hours. Thequinoline was removed under vacuum The 5-hydroxy-.l,4-bisand' ethylalcohol was added. Ethyl ether was then added and the resulting whiteprecipitate was filtered. The filtrate was concentrated under vacuum andtaken up in acetone from which it was precipitated into petroleum ether.The gummy product was precipitated twice from ethyl alcohol, once intodilute hydrochloric acid and once into water. The1,5-bis-(dhydroquinonylethylamino)- :anthraquinone melts at to C. andupon a spectrographic analysis shows the following:

s 518527 rn,a=l1,200

Example 14 1.99 g. of 1,5-dihydroxy-4,8-diaminoanthraquinone, 7.45 g. ,8hydroquinonyl-a-methyl-ethylamine-hydrobromide, 2.3 g. of sodiumbicarbonate and l'g. zinc dust were placed in 15 ml. of butanol andrefluxed under nitrogen for about 20 hours. The reaction mixture wasfiltered and poured into dilute hydrochloric acid. The resulting sludgewas precipitated twice from ethyleneglycol monomethyl ether intosaturated brine, dried very carefully and precipitated twice from ethylacetate into hexane. The product was chromatographed on aluminumsulfate, eluted first with benzene and then with ethyl acetate andevaporated to dryness. The dry product was once again precipitated fromethyl acetate into hexane and dried. A spectrographic analysis of the1,4-bis-(flhydroquinonyl a methyl-ethylamino) 5 hydroxy-S-amino-anthraquinone showed the following:

The spectrum of the product obtained would indicate that it still wasnot completely purified.

Example 15 2.5 g. of 1-nitro-anthraquinor1e and 10 g. offi-(p-aminophenyl) ethylhydroquinone 0,0 diacetate-hydrochloride weredissolved in 50 m1. of ethyleneglycol monomethyl ether and refluxed for24 hours. The reactive mixture was filtered and precipitated into 1.5%hydrochloric acid. The tarry product was purified twice fromethyleneglycol monomethyl ether into an aqueous sodium chloride-sodiumacetate solution. The precipitate was taken up in ethanol and water,deaerated with nitrogen and hydrolyzed with dilute sodium hydroxide on asteam bath for about two minutes. The product was precipitated withhydrochloric acid and purified once again from ethyleneglycol monomethylether into an aqueous sodium chloride-sodium acetate solution. Aspectrographic analysis of the 1 [p (2,5' dihydroxyphenethyl)phenylarnino]-anthraquinone showed the following:

e ;:6,40O at 503 mp Example 16 12.0 g. of quinizarin, 13 g. ofZ-aminopropylhydroquinone-hydrobromide, 4.2 g. sodium bicarbonate, 1.7g. of sodium carbonate and 17 g. of phenol were placed in 60 ml. ofethanol and 40 ml. of Water and refluxed under nitrogen for 22 hours.Then 13.1 g. of 2-aminobutylhydroquinone-hydrobromide and 4.2 g. ofsodium bicarbonate were added and the reaction mixture was refluxed foranother 24 hours under nitrogen. The reaction mixture was precipitatedinto dilute hydrochloric acid and twice purified from ethyleneglycolmonomethyl ether into saturated brine. The product was thoroughly driedand precipitated twice from ethyl acetate into hexane. A spectrographicanalysis of the l-(fl-hydroquinonyl-amethyl-ethylamino) 4 ('yhydroquinonyl a methylpropylamino)-anthraquinone produced showed thefollowing:

e =16,000 at 642 mu Example 17 9.6 g. of quinizarin, 3.5 g. ofZ-aminobutanol, 1.57 g. of sodium carbonate and 15.04 g. phenol wereplaced in 48 cc. of 95% ethanol and 32 cc. of water and refluxed 13 for30 minutes. 10.48 g. ofO-(4-methyl-2,5-dihydroxyphenyl)-a-methyl-ethylarnine-hydrobromide and3.36 g. of sodium bicarbonate were then added and refluxing wascontinued for 18 hours. The resulting product was precipitated into ahydrochloric acid solution and washed first with dilute hydrochloricacid and then with water. The precipitate was taken up indimethylformamide, precipitated into dilute hydrochloric acid, washedwith hot water and dried in a vacuum desiccator to yield a product whichmelted at 131 to 152 C. The product was further purified byprecipitation from ethyl acetate into hexane, filtration throughactivated alumina, using ethanol as an eluant, and by precipitation onceagain from ethyl acetate into hexane. A spectrographic analysis of the 1(a hydroxymethyl propylamino) 4 [fl (4'- methyl 2',5 dihydroxyphenyl) amethyl ethylaminoJ-anthraquinone produced showed the following: e642ma=18,000

An example of a photographic use of the dye developers herein disclosed,and set forth by way of illustration only, is the following:

Example 18 A photosensitive element is prepared by coating a subcoatedcellulose acetatefilm base with' a 4% aqueous gelatin solution followedby coating with a solution comprising: Cellulose acetate hydrogenphthalate g 4 Acetone cc 80 Methanol cc 20 1,4 his [/3 (3',4'dihydroxyphenyl) ethylamino]-anthraquinone g 3.5 After this coating hasdried, a silver iodobromide emulsion is applied. A liquid processingcomposition is prepared comprising: 7 Water cc 100 Sodiumcarboxymethylcellulose g 4.5 Sodium hydroxide g 1.5 Metol g 0.1

An image-receiving sheet is prepared by coating a polyvinylbutyral-coated baryta paper with a solution comprising:

N-methoxymethyl polyhexamethylene adipamide g 4 Isopropanol cc 80 Watercc 20 The photosensitive element is exposed and the liquid proc- Example19 A photosensitive element is prepared by coating a subcoated celluloseacetate film base with a 4% aqueous gelatin solution followed by coatingwith a solution comprising:

Cellulose acetate hydrogen phthalate g 4 Methyl Cellosolve cc 100 1,4his (beta hydroquinonyl ethylamino) anthraquinone g 2.5

A liquid processing composition is prepared comprising:

Water cc 100 Sodium carboxymethyl cellulose g 4.0 Sodium hydroxide g 2.0Metol g 0.1

The photosensitive element is exposed and the liquid processingcomposition spread between the photosensitive ele- 14 ment and animage-receiving element, prepared as described in Example 18, as theseelements are brought into superposed relationship. After an imbibitionperiod of approximately one minute, the image-receiving element isseparated and contains a cyan positive dye image of the photographedsubject.

Example 20 A photosensitive element is prepared as described in Example18, using 2 g. ofl-chloro-4-(betahydroquinonyl-ethylamino)-anthraquinone in lieuof thedye developer set forth in that example. A liquid processing compositionis prepared comprising:

Water Q. cc 100 Sodium hydroxide g 2.0 Metol g 0.1 Ascorbic acid g 0.2Sodium carboxymethyl cellulose g 4.5

The photosensitive element is exposed and then brought into superposedrelationship with an image-receiving element as the liquid processingcomposition is spread between said elements. The image-receiving elementis prepared by applying a polyvinyl butyral coating to a celluloseacetate-coated baryta paper followed by a coating of a solutioncomprising:

N-methoxymethyl polyhexamethylene adipamide g 4 Ethanol cc Furfurylalcohol cc 15 After an imbibition period of approximately one minute,the image-receiving element is separated and contains a pink, positivedye image of the photographed subject.

Example 21 Percent Sodium carboxymethyl cellulose 4.5 Potassium bromide0.2 Sodium hydroxide 2.0 1-phenyl-3-pyrazolidone 0.2

was spread between the photosensitive element and a nylon,image-receiving element such as used in Example 18. After an imbibitionperiod of one minute, the imagereceiving element was separated andcontained a cyan 1mage. 1

Example 22 A photosensitive element was prepared by coating agelatin-subcoated film base with an acetone-methanol solution (4 to 1 byvolume) comprising 3% of 1,4-bis-(amethylB-hydroquinonylethylamino)-anthraquinone dye developer, as prepared inExample 4, and 4% of cellulose acetate hydrogen phthalate. A silveriodobromide emulsion was applied and the resulting element was ex posedand processed in a manner similar to that employed in Example 21, exceptusing 2.5% sodium hydroxide to produce a cyan transfer image.

Example 23 A gelatin-subeoated film support was coated first with atetrahydrofuran solution comprising 3% ofl-fl-hydroquinonylethylamino-anthraquinone and 4% of cellulose acetatehydrogen phthalateand then with an iodobromide emulsion. Upon exposingand processing, in a manner similar to that employed in Example 18,except using 4% sodium hydroxide, a salmon-pink image was obtained. a

1 5 Example 24 A gelatin-subcoated film support was coated first with anacetone-methanol solution (4 to 1 by volume) comprising 3% of 1,5bis-(,B-hydroquinonylethylamino)-anthraquinone as prepared in Example13, and 4% of cellulose acetate hydrogen phthalate and then with aniodobromide emulsion. Upon processing, using an imagereceiving elementhaving a polyvinyl alcohol image-receiving layer and an aqueous solutioncomprising:

Percent Sodium carboxymethyl cellulose 4.5 Sodium hydroxide 2.0Potassium bromide 0.2 Sodium carbonate 2.0 N-methyl-p-aminophenolsulfate 0.2

as the processing composition, a magenta image was obtained.

Example 25 A gelatin-subcoated film support was coated first with anacetone-methanol (4 to 1 by volume) solution comprising 3% of 1 [fi(3,4' dihydroxyphenyl) ethylamino]-5-nitroanthraquinone and 4% ofcellulose acetate hydrogen phthalate and then with an iodobromideemulsion. Upon processing, in a manner similar to that employed inExample 21, a purple-magenta transfer image is obtained.

Example 27 A photosensitive element was prepared by coating agelatin-subcoated film support first with a 1 to 1acetonetetrahydrofuran coating solution comprising 4% of 1,5- bis (amethyl 3 hydroquinonylethylamino) anthraquinone and 4% of celluloseacetate hydrogen phthalate and then with a silver iodobromide emulsion.Upon processing, in a manner similar to that employed in Example 21,using a polyvinyl alcohol-receiving sheet, a magenta image was obtained.

Example 28 A gelatin-subcoated film support was first coated with anacetone-tetrahydrofuran coating solution (1 to 1 by volume) comprising3% of 1-,8-hydroxyethylamino-4-/3- hydroquinonylethylamino-anthraquinoneand 4% cellulose acetate hydrogen phthalate and then with a silveriodobromide emulsion. Upon exposing and processing, in a manner similarto that employed in Example 21, except using an aqueous processingsolution comprising:

Percent Sodium carboxymethyl cellulose 4.5 1-phenyl-3-pyrazolidone 0.2Sodium hydroxide 2.5 Potassium bromide 0.2 Ascorbic acid 1.0

a cyan transfer image is obtained.

' Example 29 A photosensitive element was prepared, as in Example 28,except that 3% of1-methylamino-4-[i-hydroquinonylethylamino-anthraquinone was used inplace of the be hydroxyethylamino 4 ,6 hydroquinonylethylaminoanthraquinone. Upon exposing and processing, in a manner similar to thatin Example 21, 'a cyan image was obtained.

Example 30 An acetone-tetrahydrofuran coating solution (1 to 1 byvolume) comprising 2% of cellulose acetate hydrogen phthalate and 5.5%of 1,4-bis-(a-methyl-fl-hydroquinonylethylamino) 5,8 bis benzenesulfonamido anthraquinone, as prepared in Example 6, was coated on agelatin-subcoated cellulose acetate support. When the coating had dried,a coating of an iodobromide emulsion was applied. The abovephotosensitive element was exposed and then processed by spreading anaqueous processing solution comprising:

Percent Sodium carboxymethyl cellulose 4.5 Sodium hydroxide 2.51-phenyl-3-pyrazolidone 1.0 2,5bis-ethyleneirninohydroquinone 0.456-nitrobenzimidazole 0.26

between said photosensitive element and a nylon imagereceiving element,as prepared in Example 18. After an imbibition period of approximatelyone minute, the image-receiving element was separated and contained adense blue image of the photographed subject.

Example 31 A photosensitive element, similar to that of Example 30, wasprepared using 5.0% of 1-(a-hydroxymethylpropylamino) 4 (a methyl [3hydroquinonylethylamino)-anthraquinone, as prepared in Example 8, as thedye developer. Upon processing, in a manner similar to that used inExample 30, using a processing solution comprising:

Percent Sodium hydroxide 1.5 Sodium carboxymethyl cellulose 4.5l-phenyl-3-pyrazolidone 1.2

2,5-bis-ethyleneiminohydroquinone 0.925 6-nitrobenzimidazole 0. 12

a cyan positive image of the photographed subject was obtained.

Example 32 A photosensitive element, similar to that of Example 30, wasprepared using 4% ofl,4-bis-(a-rnethyl-fi-hydroquinonylethylamino)-5,S-dihydroxyanthraquinone,as prepared in Example 7, as the dye developer. Upon developing in amanner similar to that used in Example 30, using a processing solutioncomprising:

Percent Sodium hydroxide 1.5 Sodium carboxymethyl cellulose 4.5l-phenyl-B-pyrazolidone 0.7 Tertiary-butyl hydroquinone 0.3-nitrobenzimidazole 0.126

a cyan positive image was obtained.

Example 33 A photosensitive element, similar to that of Example 30, wasprepared using 5.5% of 1,4-bis-(a-methyl-fi-hydroquinonylethylamino)- 5-hydroxy- 8 -amino-anthraquinone as the dye developer. Upon processing,in a manner similar to that used in Example 30, using a processingsolution comprising:

Percent Sodium hydroxide 2.0 Sodium carboxymethyl cellulose 4.51-phenyl-3-pyrazolidone 0.6 2,5-bis-ethyleneiminohydroquinone 0.46-ntirobenzimidazole 0.12

a cyan positive image was obtained.

Example 34 A photosensitive element, similar to that of Example 30, wasprepared using 5% of 1-(a-hydroxymethyl-pro- I pylamino)- 4-(a-methyl-B-hydroquinonylethylamino) 5,8-

17 dihydroxyanthraquinone, 0.073% of 6-nitrobenzimidazole and 2% ofResoflex R-296 (a plasticizer, produced by Cambridge Industries,Cambridge, Mass.), in the coating solution. Upon processing, in a mannersimilar to that employed in Example 33, a cyan positive image of thephotographed subject was obtained.

Example 35 A photosensitive element, similar to that of Example 34, wasprepared using 5.5% of 1,4-bis-(ot-methyl-B-hydroquinonylethylamino)-6,7-dichloroanthraquinone, 0.4% of 6-nitrobenzimidazole and 0.4% ofResofiex R-296 in the coating solution. Upon developing, in a mannersimilar to that employed in Example 32, except reducing the 6-nitrobenzimidazole in the processing solution to 0.08%, a cyan positiveimage was obtained.

Example 36 Example 37 A photosensitive element was made up similar tothat in Example 21, using 3% of 1,4-bis-(fi-hydroquinonylethylamino)leucoanthraquinone. Upon processing, in a manner similar to thatemployed in Example 21, and after allowing time for aerial oxidation, acyan image was obtained.

The dye developers of this invention are also useful in integralmultilayer photosensitive elements for use in multicolor diffusiontransfer processes. As an example of such photosensitive elements,mention may be made of the photosensitive elements disclosed and claimedin the O- pending US. application of Edwin H. Land and Howard G. Rogers,Serial No. 565,135, filed February 13, 1956, wherein at least twoselectively sensitized photosensitive strata are superposed on a singlesupport and are processed, simultaneously and without separation, with asingle common image-receiving element. A suitable arrangement of thistype comprises a support carrying a red-sensitive silver halide emulsionstratum, a green-sensitive silver halide emulsion stratum and ablue-sensitive silver halide emulsion stratum, said emulsions havingassociated therevwth, respectively, a cyan dye developer, a magenta dyedeveloper and a yellow dye developer. in one of the preferredembodiments of photosensitive elements of this type, the dye developersare disposed in separate alkalipermeable layers behind thephotosensitive silver halide emulsion stratum with which they areassociated.

The photosensitive elements within the scope of this invention may beused in roll film units which contain a plurality of photosensitiveframes. The photosensitive elements of this invention are especiallyuseful in composite roll film intended for use in a Polaroid LandCamera, sold by Polaroid Corporation, Cambridge 39, Massachusetts, or asimilar camera structure such, for example, as the camera forming thesubject matter of US. Patent No. 2,435,717, issued to Edwin H. Land onFebruary 10, 1948. In general, such composite roll films comprise aphotosensitive roll, a roll of image-receiving material and a pluralityof pods containing an aqueous alkaline processing solution. The rollsand pods are so associated with each other that, upon processing, thephotosensitive element may be superposed on the image-receivingelementand the pods may be ruptured to spread the aqueous alkalineprocessing solution between the superposed elements. The nature andconstruction of the pods used in such units are well known to the art.See, for example, U.S. Patent 1% Nos. 2,543,181 and 2,634,886, issued toEdwin H. Land.

It should be noted that certain dye developers within the scope of thisinvention may be subject to color changes as a result of pH changes inthe portion of the imagereceiving element to which they are diffused.Since the dye developer is generally rendered effective by solution inan aqueous alkaline liquid processing composition, it accordingly isnecessary to assure that the environment in which the transferred andunreacted dye developer is deposited has, or is capable of attaining,the requisite pH value affording the desired color to the diffused dyedeveloper. basic compound, such as diethylamine, in the liquidprocessing composition. if sodium hydroxide is utilized in theprocessing liquid, it becomes carbonated after processing and by contactwith the air, and this is eifective to provide the desired pH change.Further control of the pH of the transferred and unreacted dye developermay be had by utilizing an image-receiving element which is difiicultlypenetrable by alkali, for example an appropriate nylon such asN-methoxymethyl polyhexamethylene adipamide, or by the use of animage-receiving element in which an acid or an acid-forming compound,for example oleic acid, has been incorporated.

It will be noted that the liquid processing composition may, and in theabove examples does, contain one or more conventional developers, suchas Me tol, ascorbic acid, hydroquinones, 3-pyrazolidones, e.g.,1-phenyl-3-pyrazolidone (Phenidone), and1-phenyl-4,4-dimethyl-3-pyrazolidone. Although the dye developers in andof themselves can carry out the development, the conventional developersserve to accelerate and possibly initiate the action of the dyedeveloper. In certain instances, it is believed that the oxidation ofthe dye developers may involve a cross oxidation with the oxidizedconventional developers.

The dye developers of this invention may be used also in conventionalphotographic processes, such as tray or tank development of conventionalphotosensitive films, plates or papers to obtain black and white,monochromatic or toned prints or negatives. By way of example, adeveloper composition suitable for such use may comprise an aqueoussolution of approximately 1-2% of the dye developer, 1% sodiumhydroxide, 2% sodium sulfite and 0.05% potassium bromide. Afterdevelopment is completed, any unreacted dye developer is washed out ofthe photosensitive element, preferably with an alkaline washing mediumor other medium in which the unreacted dye is soluble. The expressiontoned is used to designate photographic images wherein the silver isretained with the precipitated dye, whereas monochromatic is intended todesignate dye images free of silver.

It should be noted that the dye developers of this medium areself-sufficient to provide the desired color image and do not dependupon coupling reactions to produce the desired color. They thus providea complete departure from conventional photographic color processes inwhich the color is produced by a coupling reaction between a colorformer or coupler and the oxidized developing agent, as well asso-called auto-coupling processes in which color is obtained by areaction of the oxidized developing agent with unoxidized developingagent.

It will be apparent that, by appropriate selection of theimage-receiving element from among suitable known opaque and transparentmaterials, it is possible to obtain either a colored positive reflectionprint or a colored positive transparency. Likewise, the inventiveconcepts herein set forth are adaptable for multicolor work by the useof special photographic materials, for example, film materials of thetype containing two or more photosensitized elements associated with anappropriate number of image-receiving elements and adapted to be treatedwith one or more liquid processing compositions, appropriate dyedevelopers suitable to impait the desired subtractive This may beaccomplished by use of a volatile.

19 colors being incorporated in the photosensitized elements or in theliquid processing compositions. Examples of such photographic materialsare disclosed in US. Patent No. 2,647,049 to Edwin H. Land.

As set forth above, the dye developers of this invention wherein Z islower alkylene unexpectedly provide a substantial increase in thedensity of the transfer images as compared with images produced, undersimilar conditions, using the dye developers disclosed in theabove-mentioned application Serial No. 449,514 (now abandoned), whereinthe Z group is absent. The following chart is illustrative of thisincrease in density and gives a comparison under substantially similartest conditions between some of the dye developers of this invention and1,4-bis- (2,5'-dihydroxyanilino)anthraquinone, one of the dye developersdisclosed in application Serial No. 449,514 wherein the Z group isabsent.

Compound mnx Dmln The inventive concepts herein set forth are adaptablefor the formation of colored images in accordance with the photographicproducts and processes described and claimed in the copendingapplication of Edwin H. Land, Serial No. 448,441, filed August 9, 1954,now US. Patent No. 2,968,554, issued January 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyesfor textile fibres.

In the preceding portions of the specification the expression Color hasbeen frequently used. This expression is intended to include the use ofa plurality of colors to obtain black.

The present application is concerned with the photographic products,processes and compositions and is a continuation in part of applicationSerial No. 824,785, filed July 3, 1959 (now abandoned), which in turn isa continuation in part of application Serial No. 478,922, filed December30, 1954, now abandoned.

Since certain changes may be made in the above products, compositionsand processes without departing from the scope of the invention hereininvolved, it is intended that all matter contained in the abovedescription shall be interpreted as illustrative and not in a limitingsense.

What is claimed is:

1. In a process of forming a photographic image in color, the stepswhich comprise developing an exposed silver halide emulsion with anaqueous alkaline solution containing a dye developer having ananthraquinone nucleus, at least one and not more than two of the nuclearcarbon atoms of said anthraquinone nucleus having linked directlythereto a radical of the formula:

wherein Z is a lower alkylene radical and X is a dihydroxyphenyl silverhalide developing radical, said --NH-ZX substituents containing the onlysilver halide developing radical in said dye developer, providing as afunction of the development an image-wise distribution of unoxidized dyedeveloper in undeveloped areas of said emulsion, and transferring atleast part of said distribution of said unoxidized dye developer byimbibition from said emulsion to an image-receiving layer in superposedrelationship with said emulsion to impart to said image-receiving layera positive dye image.

2. A process as defined in claim 1 wherein said aqueous alkalinesolution also contains an auxiliary silver halide developer.

Cir

3. A process as defined in claim 1 wherein said dye developer isdisposed prior to exposure in a photosensitive element comprising saidsilver halide emulsion, the anthraquinone nucleus of said dye developerbeing in its leuco form and subsequent to exposure oxidizing said leucoform to the anthraquinone form.

4. A process as defined in claim 1 wherein there are two NHZX radicalspresent in said dye developer and said NH-Z-X radicals are substitutedin the 1 and 4 positions of the anthraquinone nucleus.

5. A process as defined in claim 4 wherein X is a paradihydroxyphenylsilver halide developing radical.

6. A process as defined in claim 4 wherein X is an ortho-dihydroxyphenylsilver halide developing radical.

7. A process as defined in claim 1 wherein there is one NHZX radicalpresent in said dye developer said NHZX radical being substituted in the1 position of the anthraquinone nucleus and the 4 position of saidanthraquinone nucleus being substituted by an alkyl amino group.

8. A process as defined in claim 7 wherein the alkyl group of said alkylamino group is a hydroxy alkyl radical.

9. A process as defined in claim 8 wherein said bydroxy alkyl group is ahydroxy secondary alkyl group and the secondary carbon atom of saidhydroxy secondary alkyl group is attached to the amino group.

10. A process as defined in claim 7 wherein X is a para-dihydroxyphenylsilver halide developing radical and the alkyl group of said alkyl aminogroup comprises less than 6 carbon atoms.

11. A process as defined in claim 7 wherein X is anortho-dihydroxyphenyl silver halide developing radical and the alkylgroup of said alkyl amino comprises less than 6 carbon atoms.

12. A process as defined in claim 1 wherein said dye developer is 1,4bis- (:x-methyl-fi-hydroquinonyl-ethylamino) anthraquinone.

13. A process as defined in claim 1 wherein said dye developer is 1,4bis(a-methyl-,B-hydroquinonyl-ethylamino)5,8dihydroxyanthraquinone.

14. A process as defined in claim 1 wherein said dye developer is 1(a-hydroxymethylpropylamino)4-(amethyl-,8-hydroquinonyl-ethylamino)anthraquinone.

15. A process as defined in claim 1 wherein said dye developer is l(a-hydroxymethyl-propylamino)4-(amethyl ,8 hydroquinonyl-ethylamino)5,8-dihydroxyanthraquinone.

16. A process as defined in claim 1 wherein said dye developer is 1,4bis(a-methyl-B-hydroquinonyl-ethylamino)5,8bis-benzenesulfonamido-anthraquinone.

17. In a photographic product comprising a photosensitive element, animage-receiving layer and a rupturable container holding an aqueousalkaline processing solution, said photosensitive element being adaptedso as to be capable of being superposed on the image-receiving layer andsaid rupturable container being adapted so as to be capable of beingruptured and dispensing the aqueous alkaline processing solution betweensaid superposed photosensitive element and said image-receiving layer,the feature of disposing in said photosensitive element a dye developerhaving an antharaquinone nucleus, at least one and not more than two ofthe nuclear carbon atoms of said anthraquinone nucleus having linkeddirectly thereto a radical of the formula:

NHZ-X wherein Z is a lower alkylene radical and X is a dihydroxyphenylsilver halide developing radical, said -NHZ-X substituents containingthe only silver halide developing radical in said dye developer.

18. A photographic product as defined in claim 17 wherein there are twoNHZX radicals present in said dye developer and said NHZX radicals aresubstituted in the l and 4 positions of said anthraquinone nucleus.

19. A process of developing an exposed photosensitive silver halideemulsion which comprises developing an exposed silver halide emulsionwith an aqueous alkaline processing solution containing a dye developerhaving an anthraquinone nucleus, at least one and not more than two ofthe nuclear carbon atoms of said anthraquinone nucleus having linkeddirectly thereto a radical of the formula:

wherein Z is a lower alkylene radical and X is a dihydroxyphenyl silverhalide developing radical, said substituents containing the only silverhalide developing radical in said dye developer.

20. A process as defined in claim 19 wherein said aqueous alkalineprocessing solution also contains an auxiliary silver halide developer.

21. A process as defined in claim 19 wherein there are two NHZX radicalspresent in said dye developer and said NHZX radicals are substituted inthe 1 and 4 positions of the anthraquinone nucleus.

22. A process as defined in claim 19 wherein X is a para-dihydroxyphenylsilver halide developing radical.

23. A process as defined in claim 19 wherein X is aortho-dihydroxyphenyl silver halide developing radical.

24. A process as defined in claim 19 wherein there is one -NH-Z-Xradical present in the dye developer, said NHZX radical beingsubstituted in the 1 position of the anthraquinone nucleus and the 4position of said anthraquinone nucleus is substituted by an alkyl aminogroup.

25. A process as defined in claim 24 wherein the alkyl group of saidalkyl amino group is a hydroxy alkyl radical.

26. A process as defined in claim 25 wherein said hydroxy alkyl group isa hydroxy secondary alkyl group and the secondary carbon atom of saidhydroxy secondary alkyl group is attached to the amino group.

27. A process as defined in claim 24 wherein X is a para-dihydroxyphenylsilver halide developing radical and the alkyl group of said alkyl aminogroup comprises less than 6 carbon atoms.

28. A process as defined in claim 24 wherein X is anortho-dihydroxyphenyl silver halide developing radical and the alkylgroup of said alkyl amino group comprises less than 6 carobn atoms.

29. A photographic product comprising a plurality of layers including asilver halide emulsion layer, a layer contiguous with said silver halideemulsion layer containing a dye developer having an anthraquinonenucleus, at least one and not more than two of the nuclear carbon atomsof said anthraquinone nucleus being joined to a radical represented bythe formula:

wherein Z is a lower alkylene radical and X is a dihydroxyphenyl silverhalide developing radical, said NH-ZX substituents containing the onlysilver halide developing radical in said dye developer.

30. A photographic product as defined in claim 29 wherein there are twoNHZX radicals present in said dye developer, said NHZX radicals aresubstituted in the 1 and 4 positions of the anthraquinone nucleus and Xis a para-dihydroxyphenyl silver halide developing radical.

31. A photographic product as defined in claim 29 wherein there are twoNHZX radicals present in said dye developer, said NH-ZX radicals aresubstituted in the 1 and 4 positions of the anthraquinone nucleus and Xis an ortho-dihydroxyphenyl silver halide developing radical.

32. A photographic product as defined in claim 29 wherein there is oneNHZX radical present in said dye developer, said NH--ZX radical issubstituted in the 1 position of the anthraquinone nucleus, the 4position of said anthraquinone nucleus being substituted by an alkylamino group, said X being a paradihydroxyphenyl silver halide developingradical and the alkyl group of said alkyl amino group in the 4 positioncomprising less than 6 carbon atoms.

33. A photographic product as defined in claim 29 wherein there is one-NHZX radical present in said dye developer, said vNHZ-X radical issubstituted in the 1 position of the anthraquinone nucleus and the 4position of said anthraquinone nucleus is substituted by an alkyl aminogroup, said X radical being an orthodihydroxyphenyl silver halidedeveloping radical and the alkyl portion of said alkyl amino groupcomprising less than 6 carbon atoms.

34. A product as defined in claim 29 wherein said dye developer is1,4-biS-(oc-InetlJYl-B-hYdlOqUinOnYl ethylarnino)-anthraquinone.

35. A product as defined in claim 29 wherein said dye developer is1,4-bis-(a-methyl-B-hydroquinonyl ethylamino) -5 8-dihydroxyanthraquinone.

36. A product as defined in claim 29 wherein said dye developer is1-(u-hydroXymethyl-propylamino) 4(ccmethyl-fl-hydroquinonyl-ethylamino)-anthraquinone.

37. A product as defined in claim 29 wherein said dye developer is1-(a-hydroxymethyl-propylamino) 4 (ocmethyl-B-hydroquinonyl-ethylamino)5,8 dihydroxyanthraquinone.

38. A product as defined in claim 29 wherein said dye developer is1,4-bis-(a-methyl-B-hydroquinonyl ethylamino)-5,8-bis-benzensulfonamido) anthraquinone.

References Cited in the file of this patent UNITED STATES PATENTS2,983,600 Rogers May '9, 1961 FOREIGN PATENTS 682,665 Great Britain Nov.12, 1952 OTHER REFERENCES Venekataraman Synthetic Dyes, vol. 1, AcademicPress, N.Y. (1952), pp. 358-9.

p developer column 20, line 34, after "amino" insert group line 40, for"bis(u" read bis(@ line Id/MW UNITED STATES PATENT OFFICE CERTIFICATE 0FCORRECTION Patent No. 3, 135,606 June 2, I964 Elkan R. Blout et al.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 2, lines 69 and '70, for "prefered" read preferred column 5, line17, for "anthraquinione" read anthraqui-none column 7, line 66, for"anthraquionne" read anthraquinone column 8, line 35, for "2beta" read2-(betacolumn 10, line 2, for "to" read into line 46, for "monoethyl"read monomethyl column 11, lines 28 and 29 for "monoethyl" readmonomethyl column 13, line I, for "'0-" read column 18, line 48, after"dye" insert 50, for "-bis( 1" read -biS( 1- same column 20 line 62, for"antharaquinone" read anthraquinone column 21, line 27, for "a" read anline 49, for "carobn" read carbon column 22, line 48, for"-loenzensulfonamido) anthraquinone" read W benzenesulfonamidoanthraquinone line 52, for "2,983,600" read 2,983, 606 line 58, for"Venekataraman" read Venkataraman Signed and sealed this 3rd day ofNovember 1964,

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. IN A PROCESS OF FORMING A PHOTOGRAPHIC IMAGE IN COLOR, THE STEPSWHICH COMPRISE DEVELOPNG AN EXPOSED SILVER HALIDE EMULSION WITH ANAQUEOUS ALKALINE SOLUTION CONTAINING A DYE DEVELOPER HAVING ANANTHRAQUINONE NUCLEUS, AT LEAST ONE AND NOT MORE THAN TWO OF THE NUCLEARCARBON ATOMS OF SAID ANTHRAQUINONE NUCLUES HAVING LINKED DIRECTLYTHERETO A RADICAL OF THE FORMULA: